WO1991006118A1 - Non-photographic method for patterning organic polymer films - Google Patents

Non-photographic method for patterning organic polymer films Download PDF

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Publication number
WO1991006118A1
WO1991006118A1 PCT/US1990/005664 US9005664W WO9106118A1 WO 1991006118 A1 WO1991006118 A1 WO 1991006118A1 US 9005664 W US9005664 W US 9005664W WO 9106118 A1 WO9106118 A1 WO 9106118A1
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WIPO (PCT)
Prior art keywords
layer
patterned
solvent
organic polymer
polymer
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PCT/US1990/005664
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English (en)
French (fr)
Inventor
John James Felten
Original Assignee
E.I. Du Pont De Nemours And Company
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Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to KR1019920700903A priority Critical patent/KR960010009B1/ko
Priority to EP90917075A priority patent/EP0497896B1/en
Priority to DE69030261T priority patent/DE69030261T2/de
Priority to CA002069306A priority patent/CA2069306A1/en
Publication of WO1991006118A1 publication Critical patent/WO1991006118A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/12—Stencil printing; Silk-screen printing
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
    • C03C3/108—Glass compositions containing silica with 40% to 90% silica, by weight containing lead containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4803—Insulating or insulated parts, e.g. mountings, containers, diamond heatsinks
    • H01L21/481—Insulating layers on insulating parts, with or without metallisation
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0017—Etching of the substrate by chemical or physical means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/05—Patterning and lithography; Masks; Details of resist
    • H05K2203/0502—Patterning and lithography
    • H05K2203/0511—Diffusion patterning
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits

Definitions

  • the invention is directed to a non-photographic method for patterning organic polymer films, particularly for use in the manufacture of single layer and multilayer electronic devices such as thick film hybrids.
  • Thick film technology has historically been an attractive method of producing conductors, dielectrics, and resistors that are rugged and reliable.
  • the technology is well suited for economical production of short production runs. Its ability to be patterned in multilayer configurations has allowed fabrication of devices with extremely high circuit density.
  • the successive levels of conductors in the multilayer structure are separated by insulating dielectric layers and are interconnected by vias through the dielectric layers.
  • the multilayer approach is more expensive than a single layer approach because it requires painstaking inspection, realignment between layers, and careful processing to avoid blistering and cracking.
  • the most obvious way to reduce these problems associated with multilayer production is to reduce line and space dimensions, thereby reducing the number of layers in a given structure.
  • the problem with this approach has been the limited resolution capability of thick film screen printing, which limits the size of vias used to connect layers of circuitry to 10 to 15 mils diameter.
  • conductors are limited to a narrowest line width and spacing of 5 to 7 mil lines and spaces in production quantities.
  • the invention is therefore directed to a non- photographic method for making patterns in organic polymer films comprising the sequential steps:
  • a patterned second layer comprising an agent which is capable of changing the dispersibility of the solid organic polymer in the predetermined eluant
  • the invention can be used to make either negative or positive images.
  • the method comprises the sequential steps of:
  • a patterned second layer comprising a viscous dispersion of solid organic polymer, dispersibility-changing agent and optionally solvent, the dispersibility-changing agent (1) being a dispersant for the polymer of the first organic polymer layer and (2) having a higher atmospheric boiling point than the solvent;
  • the method comprises the sequential steps of:
  • Figure 1 is a schematic representation of the method of the invention in the negative-acting mode
  • Figure 2 is a schematic representation of the method of the invention in the positive- acting mode.
  • Figure 1 is shown schematically a negative- acting non-photographic method for making patterns in organic polymer films comprising the sequential steps:
  • a patterned second layer 5 comprising a solution of solid organic polymer, solubilizing agent and solvent, the solubilizing agent (a) being soluble in the polymer of the first organic polymer layer 3 and (b) having a higher atmospheric boiling point than the solvent;
  • a patterned second layer 15 comprising a desolubilizing agent which is capable of decreasing the solubility of the organic polymer in the solvent and is itself insoluble in the solvent;
  • the insolubilizer-depleted areas of the patterned second layer 15 are soluble in the solvent, they will be removed during the solvent-washing step. On the other hand, if the insolubilizer-depleted areas of the patterned second layer 15 are insoluble in the solvent, they will remain after the solvent-washing step.
  • liquid refers to any fluid, either liquid or gaseous, which is capable of dissolving or otherwise placing the underlying unpatterned layer into a dispersible form.
  • dispenser means with respect to a film of given material that the material is capable of displacement or removal by physical or chemical action of a wash liquid or by lifting off.
  • volatile solvent means any solvent which can be removed by evaporation at a temperature of 120C or less at one atmosphere.
  • Removal of diffusion-patterned areas of the underlying polymer layer may take place by several mechanisms such as the following:
  • the method of the invention can be used on either inorganic substrates, such as AI2O3, Si ⁇ 2, silicon, A1N and the like, or organic substrates, such as polyimides, phenoxy resins, epoxy resins and the like, or composite substrates such as filled organic polymers.
  • inorganic substrates such as AI2O3, Si ⁇ 2, silicon, A1N and the like
  • organic substrates such as polyimides, phenoxy resins, epoxy resins and the like, or composite substrates such as filled organic polymers.
  • solid organic polymers can be used as the material for either or both of the polymer layers so long as they are substantially non-crystalline and possess the appropriate solubility characteristics either per se or by the addition of solubilizing or insolubilizing agents.
  • non-crystalline polymers therefore refers to polymers having no more than about 50% crystallinity. Such substantial non-crystallinity is essential in order to facilitate the diffusion of the solubility adjusting agent in the patterned second layer (upper polymer layer) into the lower polymer layer.
  • Phenol-formaldehyde resins Cellulosic polymers Poly (vinyl acetate) Poly (vinyl butyral) Poly (vinyl chloride)
  • the method of the invention is intended primarily for use on layers of small thickness such as those used in the fabrication of electronic components.
  • the second layer polymer will range from 10 to 30 microns while the first layer polymer can be of much greater thickness from, 10 to 100 microns.
  • the thickness of the patterned layer is limited chiefly by the method of application rather than by considerations of operability.
  • the amount of solubilizing agent in the second layer must be sufficient to provide a solubilizing amount by diffusion to the underlying first layer.
  • the second layer will contain at least 10% weight solubilizing agent and may contain as much as 90% weight depending upon the solubility relationships of the respective polymers.
  • a plasticizer or other solubilizing agent may be added to the underlying first layer in order to make the polymer more susceptible to the action of the solubilizing agent which is diffused from the second polymer layer.
  • Resin and solvent appear to function best in these pastes when they are heated together to a maximum temperature of 140 degrees, then cooled to 70 degrees for addition of ionol, t-butylanthraquinone, and, optionally, the wetting agent.
  • the wetting agent may also be added in the paste preparation step below.
  • Paste Preparation The paste is prepared by thoroughly mixing the predispersed solids with the vehicle and the other organic components, then roll milling until an acceptable grind gauge is obtained (about 12/8 or better).
  • the amount of plasticizer needed for optimum functioning may also vary slightly from lot to lot of paste; hence, a small amount of plasticizer may also be withheld from the formulation before roll milling.
  • several trial formulations are made with the main plant lot, to decide on the best formulation for that particular combination of vehicle and inorganic solids.
  • Conductor Underprint a. Vehicle Preparation: The vehicle is prepared exactly as the vehicle for the dielectric underprint.
  • Paste Preparation The conductor inorganic components are thoroughly mixed with the vehicle described above and other organic components. The mixture is then roll milled to an acceptable grind gauge (about 15/8 or better). Some of the solvent, vehicle, and/or plasticizer may be withheld before roll milling, in order to optimize the amounts of those components later. Milling and formulation techniques are similar to those used for the dielectric.
  • Vehicles are prepared by predissolving the ethyl cellulose resin in a solution of plasticizer and solvent at an elevated temperature, to aid in the mixing of ingredients during paste formulation. Not all of the solvent and/or plasticizer in the final formulation are used in preparing the vehicle, since some of those components may optionally be added after roll milling, to optimize the amounts of them in the final formulation. Thus, the final formulation may not correspond exactly to the recipe given in this document. It is, however, representative of slightly varying pastes that have been prepared.
  • the patterning paste's inorganic and organic components not contained in the vehicle are thoroughly mixed with the vehicle described above.
  • the mixture is then roll milled to an acceptable grind gauge (about 15/8 or better).
  • Some of the solvent, vehicle, and/or plasticizer may be withheld before roll milling, in order to optimize the amounts of those components later. Milling and formulation techniques are similar to those used for the dielectric.
  • the dielectric pastes are typically printed twice with 200 mesh screens at one to two inches per second squeegee speed.
  • the patterning pastes are printed over the dielectric at higher speeds, since only a small part of the screen is open mesh.
  • the conductor pastes are printed with a 325 or 400 mesh screen, depending on the conductor thickness and resolution desired. Patterning pastes are likewise printed with a 325 or 400 mesh screen, to optimize the amount of plasticizer delivered to the underprint. Thinner screens and fewer prints are needed than with the dielectric, because of the thinner films typically used with conductors.
  • One of the advantages of the diffusion patterning of this invention is its ability to pattern a relatively thick underprint pattern with a thin patterning coat.
  • a patterning agent such as butyl benzyl phthalate can be used to pattern an underprint five to ten times its thickness.
  • the method can be used to make very precise thick patterns.
  • about 75-175 microns (3-7 mils) of precisely registered thick film ink would have to be deposited, while keeping via openings as small as 4 mils from flowing in.
  • patterning print Other methods of applying the patterning print are the following: (1) direct writing with a pen on a plotter to produce prototype circuit boards without generating artwork or exposing boards; (2) writing with an ink jet printhead similar to those found in commercially available computer printers; and (3) using a solid state solubility altering agent such as a compatible plasticizer, resin, acid, or base that can be toned onto the underprint, e.g. by a laser printer.
  • a solid state solubility altering agent such as a compatible plasticizer, resin, acid, or base that can be toned onto the underprint, e.g. by a laser printer.
  • the underprint by means other than screen printing, such as in a cast tape form.
  • Development of patterned parts may have to be a batch process to keep up with the throughput of the rest of the system; and firing may also have to become a batch process is large kilns to accommodate the production scale. Consequently, it will be recognized by those skilled in polymer technology that each polymer species is compatible with a large number of different types of plasticizers or non-volatile solvents. As a result, the number of suitable polymer/solvent/non-solvent combinations is legion. Following are examples of several commercially available polymers and the plasticizers and solvent/non-solvent systems with which they can be used in practicing the invention.
  • Compatible plasticizers are Triethyl Citrate, Acetyl Triethyl Citrate, epoxy type plasticizers, glycerol acetate (mono, di, tri), dimethyl adipate, tridecyl adipate, di n-hexyl azelate, ethylene glycol diacetate, diethylene glycol esters and derivatives, triethylene glycol esters (e.g. methyl, ethyl, propyl, butyl), di- and tri- propylene glycol esters.
  • long chain hydrocarbons and aromatic hydrocarbons supplied by Dover Chemical Co., New York, N.Y., tricresyl phosphate, alkyl phthalates (dimethyl through dibutyl), dimethyl sebacate, and sulfonic acid derivatives such as o- and p- toluenesulfonamide.
  • Compatible plasticizers are citric acid esters (ethyl through butyl), acetyl epoxy stearates, glycerol di- and tri ⁇ acetate, dimethyl and dibutyl adipates, tridecyl adipate, dihexyl adipate, diethylene glycol dipelargonate, dipropylene glycol caprylates and heptanoates, hydrocarbons, sucrose acetate isobutyrate, dioctyl isophthalate, glycerol monolaurate, trioctyl trimellitate, triisodecyl trimellitate, isopropyl myristate, n-butyl myristate, butyl oleate, tetrahydrofurfuryl oleate, chlorinated paraffins and derivatives, diethylene glycol dipelargonate, alkyl phosphates (triethyl through tributyl), triphenyl phosphate,
  • Plasticizers are: acid esters of abietic acid (methyl abietate), acetic acid esters (cumphenylacetate), adipic acid derivatives (e.g.
  • benzyloctyl adipate diisodecyl adipate, tridecyl adipate
  • azelaic acid esters such as diisooctyl azelate, diethylene glycol dibenzoate, triethylene glycol dibenzoate, citrates such as triethyl citrate, epoxy type plasticizers, polyvinyl methyl ethers, glycerol mono-, di-, and triacetates, ethylene glycol diacetate, polyethylene glycol 200 to 1000, phthalate esters (dimethyl to dibutyl), isophthalic acid esters (dimethyl, diisooctyl, di- 2- ethylhexyl), mellitates such as trioctyl trimellitate, isooctylisodecyl trimellitate, isopropyl myristate, methyl and propyl oleates, isopropyl and isooctyl palmitate
  • plasticizers that are compatible with cellulose nitrate are also compatible with ethyl cellulose.
  • Ethyl cellulose is thus compatible with a large number of plasticizers.
  • Some plasticizers are: acid esters of abietic acid (methyl abietate), acetic acid esters (cumphenylacetate), adipic acid derivatives (eg.
  • benzyloctyl adipate diisodecyl adipate, tridecyl adipate
  • azelaic acid esters such as diisooctyl azelate, diethylene glycol dibenzoate, triethylene glycol dibenzoate, citrates such as triethyl citrate, epoxy type plasticizers, polyvinyl methyl ethers, glycerol mono-, di-, and triacetates, ethylene glycol diacetate, polyethylene glycol 200 to 1000, phthalate esters (dimethyl to dibutyl), isophthalic acid esters (dimethyl, diisooctyl, di- 2-ethylhexyl), mellitates such as trioctyl trimellitate and isooctylisodecyl trimellitate, isopropyl myristate, methyl and propyl oleates, isopropyl and isooctyl palmitates
  • Typical plasticizers are methyl abietate, hydrogenated methyl abietate,benzyl octyl adipate, many alkyl adipates (butyl through decyl and mixed esters), azelaic acid esters such as di-(2-ethylhexyl) azelate, some benzoic acid esters such as diethylene glycol dibenzoate, citric acid derivatives such as tri-n-butyl citrate, oleic acid esters such as methyl oleate, chlorinated paraffins, alkyl and aryl phosphates such as tributyl phosphate or tricresyl phosphate, many phthalate esters such as dimethyl, dipropyl, dibutyl, or dioctyl phthalate, butyl benzyl phthalate, and other mixed alkyl and aryl phthalates. Also, ricinoleic and sebacic acid esters; some stearate
  • Plasticizers are sulfonic acid derivatives such as o- and p- toluenesulfonamide; sucrose derivatives such as sucrose octoacetate; some stearates, such as glycerol triacetoxy stearate; dibenzyl sebacate; ricinoleic acid esters; polyesters; some phthalate esters such as dibutyl and butyl benzyl phthalates; most phosphoric acid esters, such as tributyl or triphenyl phosphates; most chlorinated paraffins; glyceryl monooleate; di-n-butyl maleate; some glycol derivatives such as polyethylene glycol di-(2-ethylhexoate).
  • citric acid esters such as triethyl or tri-n-butyl citrate.
  • phthalate esters such as dimethyl, diethyl, dipropyl, dibutyl, butyl benzyl, dioctyl or dicapryl phthalate; mixed phthalates; ditridecyl phthalate; also polyesters; some ricinoleic acid esters, such as methyl acetyl ricinoleate; stearic acid esters such as glyceryl tri-acetoxy stearate. Also, o- and p-toluene-ethylsulfonamide.
  • phthalate esters such as dimethyl, diethyl, dipropyl, dibutyl, butyl benzyl, dioctyl or dicapryl phthalate; mixed phthalates; ditridecyl phthalate; also polyesters; some ricinoleic acid esters, such as methyl acetyl ricinoleate; stearic acid esters such as glyceryl fri-acetoxy stearate.
  • epoxy type plasticizers Also suitable: polyethylene glycol di-(2-ethylhexoate); dibutyl sebacate; dioctyl- and dinonyl- sebacates; and dioctyl terephthatate.
  • phthalate esters such as dimethyl, diethyl, dipropyl, dibutyl, butyl benzyl, dioctyl or dicapryl phthalate; mixed phthalates; ditridecyl phthalate; also polyesters; some ricinoleic acid esters, such as methyl acetyl ricinoleate; stearic acid esters such as glyceryl tri-acetoxy stearate.
  • epoxy type plasticizers Also suitable: polyethylene glycol di-(2-ethylhexoate); dibutyl sebacate; dioctyl- and dinonyl- sebacates; and dioctyl terephthatate.
  • Compatible plasticizers are: methyl abietate, camphor, cumphenyl acetate, octyl and nonyl adipates, dipropylene glycol dibenzoate, polyethylene glycol (200) dibenzoate, pentaerythritol tetrabenzoate, di- and triethylene glycol esters, some hydrocarbon type plasticizers, mellitic acid esters such as triisononyl trimellitate, isopropyl myristate, isopropyl oleate, ethylene glycol monobutyl ether oleate, chlorinated paraffins, phosphoric acid esters such as triethyl and tributyl phosphate, t-butyl diphenyl phosphate, tricresyl phosphate, alkyl aryl phosphates; many phthalic acid esters such as dibutyl, dipropyl, or dihexyl phthalate; also butyl benzyl
  • dibutyl or dioctyl sebacate also sebacic acid esters; sucrose benzoate; and terephthalic acid esters such as dioctyl terephthalate.
  • Camphor is also a useful plasticizer.
  • Non-Solvents Hydrocarbons, aliphatic ethers, weak mineral acids.
  • Non-Solvents Aliphatic hydrocarbons, methanol (cold), ethanol, diethyl ether.
  • Halogenated hydrocarbons ethanol/diethyl ether, acetone, methyl amyl ketone, cyclohexanone, methyl acetate, ethyl acetate, ethyl butyrate, ethyl lactate, ethylene glycol ether acetates, ethylene carbonate, furan derivatives, nitrobenzene.
  • Non-Solvents :
  • D.S. 1.0 to 1.5: Pyridine, formic acid, acetic acid, water (cold)
  • D.S. 2 Methylene chloride, chloroform, dichloroethylene, chlorohydrins, ethanol, THF.
  • D.S. 2.3 Benzene, toluene, alkyl halogenides, alcohols, furan derivatives, ketones, acetic esters, carbon disulfide, nitromethane.
  • D.S. 2.0 Hydrocarbons, carbon tetrachloride, trichloroethylene, alcohols, diethyl ether, ketones, esters, water.
  • D.S. 2.3
  • D.S. 3.0 Hydrocarbons, decalin, xylene, carbon tetrachloride, tetrahydrofurfuryl alcohol, diols, n-propyl ether.
  • Cyclohexane (>35 deg. C), cyclohexane/acetone, methylcyclohexane/acetone, decahydronaphthalene/diethyl oxalate, benzene, toluene, ethylbenzene, styrene, lower chlorinated aliphatic hydrocarbons, phenol/acetone, THF, dimethyltetrahydrofuran, dioxane, methyl ethyl ketone, dusopropyl ketone, cyclohexanone, glycol formal, ethyl acetate, butyl acetate, methyl-, ethyl-, n-butyl phthalate, 1- nitropropane, carbon disulfide, tributyl phosphate, phosphorus trichloride.
  • Non-Solvents :
  • Saturated hydrocarbons alcohols, phenol, diols, ethylene chlorohydrin, perfluorobenzene, 1,2,3,4-tetrafluorobenzene (lower than 10 deg. C), diethyl ether, glycol ethers, acetone, acetic acid, isobutyl phthalate, methylhexyl phthalate, tri(chloroethyl) phosphate, tricresyl phosphate.
  • Acetalization 70% Alcohols, cyclohexanone, ethyl lactate, ethylene glycol acetate. Acetalization 77%: Methylene chloride, alcohols, acetone, methyl ethyl ketone, cyclohexanone, lower esters, methylene chloride, alcohols, ketones, lower esters. Acetalization 83%: Methylene chloride, alcohols, ketones, lower esters.
  • Acetalization 70% Aliphatic, cycloaliphatic and aromatic hydrocarbons (sw), methylene chloride, aliphatic ketones, most esters, watrer.
  • Acetalization 77% Aliphatic, cycloaliphatic and aromatic hydrocarbons (sw), methyl isobutyl ketone, higher esters. Acetalization 83%
  • High M.W. THF, acetone/carbon disulfide, methyl ethyl ketone, cyclopentanone, cyclohexanone, DMF, nitrobenzene, DMSO.
  • Lower M.W. Toluene, xylene, methylene chloride, ethylene chloride, perchloroethylene/acetone, 1,2-dichlorobenzene, dioxane, acetone/carbon disulfide, cyclopentanone, cyclohexanone, dusopropyl ketone, mesityl oxide, isophorone, DMF, nitrobenzene, HMPT, tricresyl phosphate. Chlorinated, 63% CI:
  • Aromatic hydrocarbons Aromatic hydrocarbons, chloroform, chlorobenzene, THF, dioxane, acetone, cyclohexanone, butyl acetate, nitrobenzene, DMF, DMSO.
  • Non-solvents All M.W. 's:
  • Chloroform Chloroform, chlorobenzene, pyridine, dioxane, cyclohexanone, ethyl acetate.
  • Non-Solvents Benzene, Alcohols, diethyl ether, water.
  • Polymethylmethacrylate Solvents Dimethyl formamide, methylene chloride, chloroform, ethylene dichloride, trichloroethylene, chlorobenzene, methyl formate, ethyl acetate, isopropyl acetate, n-butyl acetate, butyl lactate, cellosolve acetate, 1,4-dioxane, tetrahydrofuran, benzene, acetone, methyl ethyl ketone, acetonitrile, nitromethane, nitroethane, 2-nitropropane, toluene, diacetone alcohol.
  • Non-solvents Dimethyl formamide, methylene chloride, chloroform, ethylene dichloride, trichloroethylene, chlorobenzene, methyl formate, ethyl acetate, isopropyl acetate, n-butyl acetate, butyl lactate, cellosolve acetate, 1,
  • Two pastes were formulated: one a dielectric paste, and one a patterning paste as follows:
  • Glass A has a D50 of ⁇ 4 to 4.5 microns; it is milled and classified to remove coarse and fine fractions. Its D 1 0 is about 1.6 microns; its D90 is 10 - 12 microns, surface area is 1.5 to 1.8 m2/g.
  • Glass B is a barium borosilicate glass used to lower the sintering temperature of the dielectric composite, due to the large particle size of glass A. Its formula follows: BaO 37.5% wt.
  • Alumina A is a 1 micron powder with a narrow particle size distribution: D10, D50, and D90 are, respectively, ⁇ 0.5, 1.1, and 2.7 microns. It is classified by settling to remove coarses and fines. Surface area is about 2.7 - 2.8 m2/g.
  • Alumina B is a 0.4 micron average particle size powder with surface area of about 5 m2/g.
  • the materials were processed by printing the dielectric optionally one, two, or three prints, with each print followed by drying 10 to 15 minutes at 80 to 90 degrees
  • the patterning layer was then printed by using a via fill screen with several sizes of via openings.
  • the patterning paste was then dried at 80 to 100 degrees C for 5 to 10 minutes.
  • the pattern was then generated in the dielectric by immersing the overprinted layers in 1.1.1-trichloroethane with ultrasonic agitation until the overprinted areas were removed and the areas under the overprinted patterning paste were dissolved away.
  • Vias as small as 5 - 7 mils were resolved in dielectric films as thick as 85 microns, with good edge definition. This is far superior both in resolution and in thickness achievable with a single patterning step with screen printing.
  • plasticizer In order to be able to pattern thicker layers, it is often advantageous to add plasticizer to the bottom layer that is to be patterned. A convenient way to determine the optimum level is to make a concentration ladder using plasticizer at different concentrations in the composition to be patterned.
  • the paste was printed and processed as in Example 1, to determine the best operating region.
  • the best region is seen to be between 2.5 and 3.5%. Inside that formulating region, a 40-50 micron thick film is seen to be satisfactorily processable. A relatively high plasticizer level in the operable region lowers development time, and increases throughput.
  • a conductor paste was formulated with copper, as follows:
  • the copper paste was prepared from the above ingredients by techniques familiar to those skilled in thick film paste formulation, and prepared for printing.
  • One coat of the conductor composition was printed onto alumina substrates through a 325 mesh screen and a negative of a screen printed conductor pattern was printed on top of the copper print, using the Patterning paste in Example 1. Both prints were dried at 85 - 95 degrees C. Dried parts were then immersed in chlorothene with ultrasound agitation for 15 - 25 seconds to generate the desired pattern. Parts were then fired. Precise four mil line/space patterns were generated. Fired parts were 10 - 12 microns thick, with a resistivity of about 3 milliohms/square. Four mil lines/space resolution is difficult, if not impossible, to achieve, in a pattern with 3 milliohms/square. In addition, the topography of the 4 mil lines is superior to screen printed parts, with more precise edge definition, and flat surfaces on the tops of conductor fingers. Three mil lines were resolved when the underprint was applied through a 400 mesh screen yielding a somewhat thinner undercoat.
  • the above formulation was prepared in the usual manner known to a person skilled in thick film formulation.
  • the gold composition was printed with a single coat through a
  • Example ' A positive working conductor paste system was formulated in copper, as follows:
  • Copper Positive Working Patterning Paste Copper Powder 3-4 micron 46.00 grams Glass Powder C 1.25
  • the copper pastes were prepared from the above ingredients by techniques familiar to those skilled in thick film paste formulation, and prepared for printing.
  • One coat of the conductor composition was printed onto alumina substrates through a 325 mesh screen; a negative of a screen printed conductor pattern was then printed on top of the copper print, using the Patterning paste in this Example. Both prints were dried at 85-95 degrees C. Dried parts were then immersed in a 1% potassium carbonate aqueous solution with ultrasound agitation for 5-15 seconds to generate the desired pattern. Precise four mil line/space patterns were generated. Dried parts were 49 microns thick. In addition, the 4 mil lines had more precise edge definition than screen- printed parts.
  • a clearly resolved printing pattern on a flexographic printing plate was transferred to a DP dielectric formulation as follows.
  • a thin film of butyl benzyl phthalate plasticizer was spread onto a flexographic printing plate that had been imaged with a test pattern.
  • the plate was then rolled over the surface of a ceramic part coated with a dried dielectric composition (See Example 1).
  • the plasticizer that was transferred from the plate to the dielectric was then diffused into the dielectric by drying for 5 minutes in an oven at 95 degrees C.
  • the image in the dielectric was developed by immersion in an ultrasonic bath containing 1.1.1-trichloroethane Chlorothene. The pattern from the plate could clearly be seen in the dielectric, thus demonstrating the capability of other techniques of plasticizer deposition to produce diffusion-patterned images.
  • the pattern may be positive or negative working- i.e. the area under the overprint may either be solubilized, as in Examples 1-4 or it may be insolubilized, for example by overprinting an aqueously developable polymer with a water incompatible plasticizer to protect the areas underneath, then removing the unplasticized material by aqueous solubilization.
  • methyl and ethyl methacrylate may be combined to allow positive or negative working resists.
  • plasticizers such as triethylene glycol would produce a negative working resist in ethanol pattern generating solvent.
  • polyesters may be patterned in a similar manner: One merely needs to determine a solubilizer or desolubilizer and a suitable pattern generating solvent. If no solubility envelope exists for a highly crosslinked polymer, that polymer would not be a likely candidate for the process.
  • a positive-working diffusion patterning system with epoxy resins can be devised as follows: A prepolymer is formed, for example, by condensation polymerising the sodium salt of bisphenol A with epichlorohydrin, as the resin in the screen printed underprinted coat to be patterned. The degree of polymerization of the prepolymer should be about 12 units long.
  • the crosslinking amine or polybasic anhydride such as diethylenetriamine or ethylenediamine, or succinic acid diahnydride, is added to the overprint paste.
  • the overprint paste is then printed onto the underprint.
  • the composite is then cured; the areas under the overprinted amine containing paste are crosslinked, insolubilizing them, and allowing the remaining material to be washed away in a suitable solvent such as trichloroe thane.
  • a negative- working polyimide diffusion patterning system can be prepared by using an incompletely cured system containing, for example, pyromellitic dianhydride (PMDA) and oxydianiline (ODA).
  • PMDA pyromellitic dianhydride
  • ODA oxydianiline
  • the incompletely cured polymer is used as the underprint; a paste containing a base such as triethanolamine or, paniculate potassium carbonate, is overprinted as the patterning print. The material is then washed in water or weak base to remove areas under the overprint.
  • a first dielectric thick-film paste was formulated using polymethyl methacrylate as the binder component of the organic medium and an overlying thick film paste containing ethyl cellulose as the binder component and a small amount of platinum acetylacetonate to serve as a decomposition catalyst.
  • the first paste was printed through an 80 mesh screen onto several alumina substrates to form 22 ⁇ m thick films (after firing) and the second paste was printed onto the first paste with a test screen having vias patterns ranging from 5 to 30 mils.
  • the printed layer assemblages were then heated to various temperatures ranging from 240 to 360C for 20 minutes and cooled, after which each was washed with an aqueous spray. Seven mil vias were resolved. It was observed that heating within the range of 280 to 320C produced the most uniform vias without erosion of the film surface.
  • the composition of the pastes was as follows:
  • a calcium zinc silicate glass was formulated with a cellulosic vehicle and 3% butyl benzyl phthlate.
  • a film of each paste was screen printed onto an alumina substrate and dried at 95-lOOC.
  • a patterning paste containing 7g alumina, 3.5g Tergitol® TMN-6, 3.15g of terpineol isomers and 0.35g ethyl cellulose was screen printed onto the dried dielectric paste layers and heated at 95-100C to dry the overprinted paste and to effect diffusion of the Tergitol detergent into the underlying dielectric layer. When the dried layer was washed under tap water, six mil vias were clearly resolved. In subsequent tests, it was shown that the use of additional plasticizer in the underlying polymer layer improved resolution still further.
  • dielectric paste B contained buytl benzal phthlate
  • dielectric paste A contained more volatile dip phthlate plasticizer.
  • composition of dielectric paste A was the same as Example 7 above and the composition of dielectric paste B was identical except that dipropyl phthalate, a more volatile plasticizer, was used in place of dibutyl benzol phthalate.
  • the composition of the patterning paste was the same as Example 7, except that it contained no pt acetylacetonate.
  • Both of the dielectric pastes were printed with screen opening of 6-11 mils and then dried at 80-85C for 12 minutes.
  • the patterning paste was then printed over the dried dielectric layers and heated to 95-100C for 10 minutes to dry the layer and to effect diffusion of the plasticizers into the underlined dielectric layers.
  • the assemblages were then developed for 10-15 seconds in a chlorothene spray after which they were rinsed with water and dried with an air knife. Upon measurement of the vias produced in each assemblage, it was shown that the vias from the dielectric layers containing the more volatile plasticizer were uniformly closer in size to the opening of the printing screens used for applying the patterning layer.

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PCT/US1990/005664 1989-10-20 1990-10-11 Non-photographic method for patterning organic polymer films WO1991006118A1 (en)

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EP90917075A EP0497896B1 (en) 1989-10-20 1990-10-11 Non-photographic method for patterning organic polymer films
DE69030261T DE69030261T2 (de) 1989-10-20 1990-10-11 Nichtphotographisches verfahren zur strukturierung organischer polymerfilme
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EP0568853A1 (en) * 1992-05-07 1993-11-10 E.I. Du Pont De Nemours And Company Photoenhanced diffusion patterning for organic polymer films
EP0583714A2 (en) * 1992-08-14 1994-02-23 E.I. Du Pont De Nemours And Company Method for preparing high-resolution wash-off images and non-photosensitive elements for use therein
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US5635334A (en) * 1992-08-21 1997-06-03 E. I. Du Pont De Nemours And Company Process for making plasma display apparatus with pixel ridges made of diffusion patterned dielectrics
US5654354A (en) * 1991-11-14 1997-08-05 E. I. Du Pont De Nemours And Company Compositions for diffusion patterning

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Publication number Priority date Publication date Assignee Title
US5306756A (en) * 1991-09-30 1994-04-26 E. I. Du Pont De Nemours And Company Method and compositions for diffusion patterning
WO1993007640A1 (en) * 1991-09-30 1993-04-15 E.I. Du Pont De Nemours And Company Method and compositions for diffusion patterning
US5275689A (en) * 1991-11-14 1994-01-04 E. I. Du Pont De Nemours And Company Method and compositions for diffusion patterning
EP0541969A1 (en) * 1991-11-14 1993-05-19 E.I. Du Pont De Nemours And Company Method and compositions for diffusion patterning
CN1042074C (zh) * 1991-11-14 1999-02-10 E·I·内穆尔杜邦公司 用于扩散法制图的方法及组合物
US5654354A (en) * 1991-11-14 1997-08-05 E. I. Du Pont De Nemours And Company Compositions for diffusion patterning
EP0568853A1 (en) * 1992-05-07 1993-11-10 E.I. Du Pont De Nemours And Company Photoenhanced diffusion patterning for organic polymer films
EP0583714A2 (en) * 1992-08-14 1994-02-23 E.I. Du Pont De Nemours And Company Method for preparing high-resolution wash-off images and non-photosensitive elements for use therein
EP0583714A3 (en) * 1992-08-14 1994-09-28 Du Pont Method for preparing high-resolution wash-off images and non-photosensitive elements for use therein
US5635334A (en) * 1992-08-21 1997-06-03 E. I. Du Pont De Nemours And Company Process for making plasma display apparatus with pixel ridges made of diffusion patterned dielectrics
EP0586943A1 (en) * 1992-08-21 1994-03-16 E.I. Du Pont De Nemours And Company Plasma display apparatus and process of making the same
EP0603743A2 (en) * 1992-12-22 1994-06-29 E.I. Du Pont De Nemours & Company Incorporated Method for preparing negative-working wash-off relief images and elements for use therein
EP0603743A3 (en) * 1992-12-22 1994-11-02 Du Pont Process for generating negative working washable relief images and elements therefor.
EP0613166A1 (en) * 1993-02-26 1994-08-31 E.I. Du Pont De Nemours And Company Method of making plasma display apparatus
EP0742572A2 (en) * 1993-02-26 1996-11-13 E.I. Du Pont De Nemours And Company Method of making plasma display apparatus
EP0742572A3 (es) * 1993-02-26 1996-12-04 Du Pont
US5385631A (en) * 1993-02-26 1995-01-31 E. I. Du Pont De Nemours And Company Method of making plasma display apparatus
WO1996000931A1 (en) * 1994-06-29 1996-01-11 E.I. Du Pont De Nemours And Company Method for preparing negative-working wash-off relief images and non-photosensitive elements for use therein
EP0742585A1 (en) * 1995-05-08 1996-11-13 E.I. Du Pont De Nemours And Company Method and compositions for diffusion patterning tape on substrate

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